Thermoplastic resin composition having improved bend/wrinkle resistant properties and formed article thereof

ABSTRACT

A thermoplastic resin composition includes 7% to 64% by mass of rubber-containing graft copolymer (A), 2% to 35% by mass of thermoplastic elastomer (B), 0.5% to 90% by mass of polycarbonate-based resins (C), and 0.5% to 20% by mass of inorganic compound (D) having volume average particle diameter (MV) of 1 to 200 μm (where a total of (A), (B), (C), and (D) (hereafter referred to as “total of a component (A) to a component (D)”) is 100% by mass). The rubber-containing graft copolymer (A) is a graft copolymer in which 35 to 80 parts by mass of rubber-like polymer selected from diene-based rubber, acrylic rubber, and ethylene-based rubber is graft-polymerized with 20 to 65 parts by mass of vinyl-based monomer mixture containing an aromatic-vinyl-based monomer and a vinyl-cyanide-based monomer (where a total of the rubber-like polymer and the vinyl-based monomer mixture is 100% by mass).

CROSS-REFERENCE TO RELATED APPLICATION

This is a divisional patent application of Ser. No. 17/616,910 filed onDec. 6, 2021, which is a PCT International Application ofPCT/JP2021/014187 filed on Apr. 1, 2021, claiming priorities of JapanesePatent Applications No. 2020-069838 field on Apr. 8, 2020 and No.2020-140258 filed on Aug. 21, 2020, the disclosures of which areincorporated by reference herein in its entireties.

TECHNICAL FIELD

The present invention relates to a thermoplastic resin compositioncapable of realizing a formed article having excellent formability,undergoing no peeling nor whitening, acquiring excellent formed-articleappearance, mechanical properties, and weld strength, having bendingperformance so that no wrinkles occur due to bending and that thebending property is maintained against repetitions, and having slipresistance and high grip performance. The present invention also relatesto a formed article produced by forming the thermoplastic resincomposition.

BACKGROUND ART

Rubber-reinforced aromatic-vinyl-based resins typified by ABS resinshave an excellent physical-property balance between impact resistanceand formability and excellent formed article appearance and, therefore,are widely used for OA equipment, home appliances, sundry goods,construction materials, and the like.

Of these, OA equipment such as personal computers and printers and homeappliances such as cameras, videos, vacuum cleaners, and washingmachines, which are frequently used or operated with hand, and carinterior parts such as door trims and glove boxes, which are frequentlytouched with passenger bodies, are required to have favorable feelingssuch as cushioning properties and hand feeling while stiffness of thepart is maintained.

To satisfy such requirements, some products are produced by bonding afacing material having flexibility to a core member having stiffness andperforming slush molding or the like. However, since the slush moldingincludes a large number of steps and raw materials are expensive, theslush molding is used for producing just some products (refer to PTL 1).

It is known that a formed article having an excellent surface touchfeeling due to not only having excellent mechanical strength and formedarticle appearance, but also having high cushioning properties, highlysoft touch feeling, and reduced feeling of stickiness is obtained bymixing a thermoplastic elastomer to a rubber-reinforcedaromatic-vinyl-base resin having a rubber portion composed of adiene-based resin and silicone rubber or ethylene.α-olefin-based rubber(refer to PTL 2 and PTL 3). However, a formed article having excellentsurface glossiness and having slip resistance and touch feelingexcellent in grip feeling has not been obtained.

PTL 4 proposes a formed article that is composed of a thermoplasticresin composition containing a specific rubber-reinforced vinyl-baseresin and a thermoplastic elastomer and that has an MIU value of 0.4 ormore as a thermoplastic resin formed article having excellent mechanicalstrength and formed article appearance such as surface glossiness andhaving slip resistance and touch feeling excellent in grip feeling.However, this thermoplastic resin formed article is not sufficient inthe performance, such as repetitive bending property, and a furtherimprovement in the strength of a formed article for a casing is desired.

PTL 1: Jp 2013-159122 A

PTL 2: Jp 2016-199729 A

PTL 3: Jp 2017-8227 A

PTL 4: Jp 2019-73645 A

SUMMARY OF INVENTION

It is an object of the present invention to provide a thermoplasticresin composition capable of realizing a formed article having excellentformability, undergoing no peeling nor whitening, acquiring excellentformed-article appearance, mechanical properties, and weld strength,having bending performance so that no wrinkles occur due to bending andso that the bending property is maintained against repetitions, andhaving slip resistance and high grip performance and to provide a formedarticle thereof.

The present inventor found that the above-described object can beachieved by a thermoplastic resin composition containing arubber-containing graft copolymer (A), a thermoplastic elastomer (B),another thermoplastic resin (C), and an inorganic compound (D) at aspecific ratio.

The scope of the present invention is as described below.

[1] A thermoplastic resin composition comprising 7% to 64% by mass ofrubber-containing graft copolymer (A), 2% to 35% by mass ofthermoplastic elastomer (B), 0.5% to 90% by mass of anotherthermoplastic resin (C), and 0.5% to 20% by mass of inorganic compound(D) (where a total of (A), (B), (C), and (D) (hereafter referred to as“total of a component (A) to a component (D)”) is 100% by mass),

wherein the rubber-containing graft copolymer (A) is a graft copolymerin which 35 to 80 parts by mass of rubber-like polymer (a1) isgraft-polymerized with 20 to 65 parts by mass of vinyl-based monomermixture (a2) containing an aromatic-vinyl-based monomer and avinyl-cyanide-based monomer (where a total of the rubber-like polymer(a1) and the vinyl-based monomer mixture (a2) is 100% by mass),

the content of the rubber-like polymer (a1) in the total 100% by mass ofthe component (A) to the component (D) is 2% to 35% by mass, and

a difference between the content (% by mass) of the rubber-like polymer(a1) in the total 100% by mass of the component (A) to the component (D)and the content (% by mass) of the thermoplastic elastomer (B) is within15% by mass.

[2] The thermoplastic resin composition according to [1], wherein theanother thermoplastic resin (C) is at least one selected from a groupconsisting of acrylonitrile-styrene-based resins, polycarbonate-basedresins, polyacrylic resins, and polybutylene-terephthalate-based resins.[3] The thermoplastic resin composition according to [1] or [2], whereinthe volume average particle diameter of the rubber-like polymer (a1) is100 to 1,500 nm, the ratio of the aromatic-vinyl-based monomer to thevinyl-cyanide-based monomer in 100% by mass of the vinyl-based monomermixture (a2) is aromatic-vinyl-based monomer/vinyl-cyanide-basedmonomer=50% to 95% by mass/50% to 5% by mass, and the graft rate of therubber-containing graft copolymer (A) is 20% to 100% by mass.[4] The thermoplastic resin composition according to any one of [1] to[3], wherein the MFR (200° C., 49.0 N) of the thermoplastic elastomer(B) is 1 to 25 g/10 min, and the MFR (230° C., 21.2 N) is 3 to 30 g/10min.[5] The thermoplastic resin composition according to any one of [1] to[4], wherein the thermoplastic elastomer (B) is a block copolymercontaining at least one polymer block P of an aromatic vinyl compoundand at least one polymer block Q of a conjugated diene compound and/or ahydrogenation product thereof and is a styrene-based elastomer having amass average particle diameter of 10,000 to 800,000, a content of thepolymer block P of 5% to 60% by mass, and a content of the polymer blockQ of 95% to 40% by mass.[6] The thermoplastic resin composition according to any one of [1] to[5], wherein the inorganic compound (D) is muscovite.[7] A thermoplastic resin formed article produced by forming thethermoplastic resin composition according to any one of [1] to [6].

Advantageous Effects of Invention

According to the thermoplastic resin composition of the presentinvention, a thermoplastic resin composition capable of realizing aformed article having excellent formability, undergoing no peeling norwhitening, acquiring excellent formed-article appearance, mechanicalproperties, and weld strength, having bending performance so that nowrinkles occur due to bending and so that the bending property ismaintained against repetitions, and having slip resistance and high gripperformance and a formed article thereof can be provided.

DESCRIPTION OF EMBODIMENTS

The embodiment according to the present invention will be describedbelow in detail.

In the present specification, “formed article” denotes a productobtained by forming a thermoplastic resin composition.

“Unit” denotes a structural portion derived from a monomer compoundbefore polymerization and introduced into a polymer or a copolymer. Forexample, “aromatic-vinyl-based monomer unit” denotes “structural portionderived from an aromatic-vinyl-based monomer and introduced into apolymer or a copolymer”.

“(Meth)acrylic acid” denotes one of or both “acrylic acid” and“methacrylic acid”.

[Thermoplastic Resin Composition]

The thermoplastic resin composition according to the present inventionis a thermoplastic resin composition containing a rubber-containinggraft copolymer (A) (hereafter also referred to as “component (A)”), athermoplastic elastomer (B) (hereafter also referred to as “component(B)”), another thermoplastic resin (C) other than the rubber-containinggraft copolymer (A) and the thermoplastic elastomer (B) (hereafter alsoreferred to as “component (C)”), and an inorganic compound (D)(hereafter also referred to as “component (D)”) at a specific ratio.

[Rubber-Containing Graft Copolymer (A)]

The rubber-containing graft copolymer (A) is produced bygraft-polymerizing a vinyl-based monomer mixture (a2) in the presence ofa rubber-like polymer (a1).

<Rubber-Like Polymer (a1)>

There is no particular limitation regarding the rubber-like polymer (a1)(hereafter also referred to as “component (a1)”) constituting therubber-containing graft copolymer (A), and examples include diene-basedrubber, acrylic rubber, and ethylene-based rubber.

Specific examples include polybutadienes, poly(butadiene-styrene)s,poly(butadiene-acrylonitrile)s, polyisoprenes, poly(butadiene-butylacrylate)s, poly(butadiene-methyl acrylate)s,poly(butadiene-methacrylate)s, poly(butadiene-ethyl acrylate)s,ethylene-propylene rubber, ethylene-propylene-diene rubber,poly(ethylene-isobutylene)s, poly(ethylene-methyl acrylate)s, andpoly(ethylene-ethyl acrylate)s.

These rubber-like polymers are used alone, or at least two types areused in combination.

Of these, polybutadienes and styrene-butadiene copolymer rubber areparticularly preferably used from the viewpoint of improving the impactresistance.

The volume average particle diameter of the rubber-like polymer (a1) ispreferably 100 to 1,500 nm, further preferably 150 to 1,000 nm, and morepreferably 200 to 500 nm from the viewpoint of impact resistance,formability, fluidity, and appearance of the resulting thermoplasticresin composition.

The volume average particle diameter of the rubber-like polymer (a1) isa value measured by a method described in the example later.

<Vinyl-Based Monomer Mixture (a2)>

A vinyl-based monomer mixture (a2) (hereafter also referred to as“component (a2)”) is a vinyl-based monomer mixture containing at leastan aromatic-vinyl-based monomer and a vinyl-cyanide-based monomer.

Examples of the aromatic-vinyl-based monomer include styrene,α-methylstyrene, p-methylstyrene, vinyltoluene, t-butylstyrene,o-ethylstyrene, o-chlorostyrene, and o,p-dichlorostyrene.

These may be used alone, or at least two types may be used incombination.

Examples of the vinyl-cyanide-based monomer include acrylonitrile,methacrylonitrile, and ethacrylonitrile. In particular, acrylonitrile ispreferable.

The vinyl-cyanide-based monomers may be used alone, or at least twotypes may be used in combination.

The ratio of the aromatic-vinyl-based monomer to the vinyl-cyanide-basedmonomer in 100% by mass of the vinyl-based monomer mixture (a2) ispreferably aromatic-vinyl-based monomer/vinyl-cyanide-based monomer=50%to 95% by mass/50% to 5% by mass, more preferably 60% to 85% by mass/40%to 15% by mass, and further preferably 65% to 80% by mass/35% to 20% bymass from the viewpoint of the formability and the formed articleappearance.

The vinyl-based monomer mixture (a2) may include, in addition to thearomatic-vinyl-based monomer and the vinyl-cyanide-based monomer,another vinyl-based monomer copolymerizable with these in the range of0% to 30% by mass. Examples of the another vinyl-based monomercopolymerizable with these include at least one of unsaturatedcarboxylic acid ester-based monomers, such as methyl (meth)acrylate,maleimide compounds, such as N-methylmaleimide, N-cyclohexylmaleimide,and N-phenylmaleimide, unsaturated dicarboxylic acids, such as maleicacid, unsaturated dicarboxylic acid anhydrides, such as maleicanhydride, and unsaturated amides, such as acrylamide, but thevinyl-based monomer is not limited to these. Of these, methyl(meth)acrylate, N-phenylmaleimide, and maleic anhydride are preferable.

<Proportion of Rubber-Like Polymer (a1) and Vinyl-Based Monomer Mixture(a2)>

The rubber-containing graft copolymer (A) is produced bygraft-polymerizing 20% to 65% by mass of vinyl-based monomer mixture(a2) in the presence of 35% to 80% by mass of rubber-like polymer (a1).In this regard, the total of the rubber-like polymer (a1) and thevinyl-based monomer mixture (a2) is 100% by mass.

When the rubber-like polymer (a1) is less than 35% by mass, and thevinyl-based monomer mixture (a2) is more than 65% by mass, the weldstrength and the wrinkling resistance are poor. When the rubber-likepolymer (a1) is more than 80% by mass, and the vinyl-based monomermixture (a2) is less than 20% by mass, the formability and the thermalstability during forming deteriorate. The proportion of the rubber-likepolymer (a1) is preferably 45% to 78% by mass and more preferably 53% to73% by mass. The proportion of the vinyl-based monomer mixture (a2) ispreferably 22% to 55% by mass and more preferably 27% to 47% by mass.

The entire amount of the vinyl-based monomer mixture (a2) is notnecessarily grafted, and the rubber-containing graft copolymer (A)obtained as a mixture with a copolymer that is not grafted is usedusually. This mixture is essentially a composition but is included inthe rubber-containing graft copolymer (A) in the present invention.

There is no particular limitation regarding the graft rate of therubber-containing graft copolymer (A), but, from the viewpoint of theimpact resistance, the graft rate is preferably 20% to 100% by mass,more preferably 30% to 80% by mass, and further preferably 40% to 70% bymass.

The graft rate of the rubber-containing graft copolymer (A) is measuredby a method described in the example later.

There is no particular limitation regarding the method forgraft-polymerizing the rubber-containing graft copolymer (A), andproduction can be performed by using any known method, such as anemulsion polymerization method, a suspension polymerization method, acontinuous bulk polymerization method, and a continuous solutionpolymerization method. Preferably, the rubber-containing graft copolymer(A) is produced by using an emulsion polymerization method or a bulkpolymerization method. Since the emulsifier content and the amount ofwater in the rubber-containing graft copolymer (A) are readily adjusted,it is most preferable that the rubber-containing graft copolymer (A) beproduced by using the emulsion polymerization method.

Regarding the thermoplastic resin composition according to the presentinvention, the content of the component (A) in the total 100% by mass ofthe component (A) to the component (D) is 7% to 64% by mass, preferably10% to 55% by mass, and more preferably 15% to 52% by mass. When thecontent of the component (A) is more than or equal to theabove-described lower limit, the weld strength and the weld retentionrate are favorable. When the content of the component (A) is less thanor equal to the above-described upper limit, the formability isfavorable.

The content of the rubber-like polymer (a1) in 100% by mass of thethermoplastic resin composition is 2% to 35% by mass, preferably 5% to35% by mass, and more preferably 8% to 33% by mass. When the content ofthe rubber-like polymer (a1) is more than or equal to theabove-described lower limit, the touch feeling (grip performance), theslip resistance, and the weld strength are favorable. When the contentof the rubber-like polymer (a1) is less than or equal to theabove-described upper limit, the formability is favorable.

[Thermoplastic Elastomer (B)]

There is no particular limitation regarding the thermoplastic elastomer(B) used in the present invention provided that the polymer can producea formed article having rubber elasticity by forming throughheat-melting. The thermoplastic elastomer (B) can be formed throughheat-melting, but the diene-based rubber and the non-diene-based rubberused in the component (a1) cannot be formed through heat-melting.Therefore, the two differ from each other.

The MFR (200° C., 49.0 N) of the thermoplastic elastomer (B) ispreferably 1 to 25 g/10 min and more preferably 2 to 15 g/10 min.

The MFR (230° C., 21.2 N) of the thermoplastic elastomer (B) ispreferably 3 to 30 g/10 min and more preferably 5 to 20 g/10 min.

Specific examples of the thermoplastic elastomer (B) includestyrene-based elastomers, diene-based elastomers, such aspolybutadiene-based elastomers, olefin-based elastomers, urethane-basedelastomers, polyvinylchloride-based elastomers, ester-based elastomers,fluororesin-based elastomers, and ion-crosslinked elastomers (ionomers).These thermoplastic elastomers may be used alone, or at least two typesmay be used in combination.

Of these, styrene-based elastomers and diene-based elastomers, such aspolybutadiene-based elastomers, are favorable from the viewpoint of thetouch feeling (grip feeling) and the slip resistance.

Specific examples of the styrene-based elastomer include blockcopolymers containing at least one polymer block P of an aromatic vinylcompound and at least one polymer block Q of a conjugated diene compoundand hydrogenation products thereof. The polymer block P and the polymerblock Q may be bonded in a straight chain type or may be bonded in aradial type.

The polymer block Q may be a random copolymer containing a small amountof aromatic vinyl compound as a constituent unit or may be a so-calledtaper-type block in which the content of the constituent unit derivedfrom an organic vinyl compound gradually increases.

There is no particular limitation regarding the structure of the blockcopolymer, and any one of (P-Q)n type, (P-Q)n-A type, and (P-Q)n-C typecan be adopted.

In the formulae, P represents a polymer block of an aromatic vinylcompound, Q represents a polymer block of a conjugated diene compound, Crepresents a coupling agent residue, and n represents an integer of 1 ormore.

Regarding the aromatic vinyl compound serving as the constituent unit ofthe polymer block P of the styrene-based elastomer, all aromatic vinylcompounds listed as the vinyl-based monomer of the above-describedcomponent (a2) may be used, and styrene is preferably used.

These aromatic vinyl compounds may be used alone, or at least two typesmay be used in combination.

Examples of the conjugated diene compound serving as the constituentunit of the polymer block Q of the styrene-based elastomer include1,3-butadiene, isoprene, 2-methyl-1,3-butadiene, 2,3-diethyl-butadiene,2-neopentyl-1,3-butadiene, 2-chloro-1,3-butadiene,2-cyano-1,3-butadiene, substituted straight-chain conjugatedpentadienes, and straight-chain or side-chain conjugated hexadienes. Ofthese, 1,3-butadiene, isoprene, and 2-methyl-1,3-butadiene arepreferable.

These conjugated diene compounds may be used alone, or at least twotypes may be used in combination.

The content of the polymer block P of the styrene-based elastomer ispreferably 5% to 60% by mass and more preferably 15% to 50% by mass. Thecontent of the polymer block Q of the styrene-based elastomer ispreferably 95% to 40% by mass and more preferably 85% to 50% by mass.When the contents of the polymer blocks P and Q are within theabove-described ranges, the touch feeling (grip feeling) and the slipresistance are favorable.

The styrene-based elastomer that is not hydrogenated and that iscomposed of the above-described block copolymer can be produced throughblock copolymerization by using a common method. The hydrogenatedproduct of the block copolymer can be obtained by subjecting the polymerblock Q of the conjugated diene compound obtained as described above toa hydrogenation reaction by using a known method. Specific methodsinclude methods described in JP 42-8704 B, JP 43-6636 B, JP 63-4841 B,JP 63-5401 B, JP 2-133406 A, and JP 1-297413 A.

Regarding the hydrogenation reaction, when a conjugated-diene-basedpolymer in which the polymer block Q is a polymer block of 1,3-butadieneis nonselectively hydrogenated, ethylene is generated from a portionpolymerized through 1,4-vinyl bonding, and butylene is generated from aportion polymerized through 1,2-vinyl bonding, so that astyrene-ethylene-butylene-styrene copolymer (SEBS) and the like aregenerated as hydrogenation products. When a 1,2-vinyl bond isselectively hydrogenated, a styrene-butadiene-butylene-styrene copolymer(SBBS) and the like are generated as hydrogenation products.

Preferable examples of the styrene-based elastomer include astyrene-butadiene-styrene block copolymer (SBS), astyrene-ethylene-butylene-styrene copolymer (SEBS), astyrene-butadiene-butylene-styrene copolymer (SBBS), and astyrene-isoprene-styrene copolymer (SIS). Of these, in particular, astyrene-ethylene-butylene-styrene copolymer (SEBS) is favorable from theviewpoint of the touch feeling (grip feeling) and the slip resistance.

Commercially available products may be used as SEBS. Examples of thecommercially available product serving as SEBS include DYNARON Series(trade name, produced by JSR Corporation), RABALON Series (trade name,produced by MITSUBISHI CHEMICAL CORPORATION), Tuftec Series (trade name,produced by Asahi Kasei Corporation), and TPE-SB Series (trade name,produced by Sumitomo Chemical Co., Ltd.).

Examples of the thermoplastic elastomer (B) other than the styrene-basedelastomer include high cis- and low cis-butadiene rubber (BR), highcis-isoprene rubber (IR), emulsification polymerization and solutionpolymerization styrene-butadiene rubber (SBR), acrylonitrile-butadienerubber (NBR), ethylene-propylene rubber (EPM, EPDM), chloroprene rubber,butyl rubber, and natural rubber (NR).

The thermoplastic elastomers (B) such as styrene-based elastomers may beused alone, or at least two types that differ from each other inelastomer species, structure, constituent unit, physical properties, orthe like may be used in combination.

Regarding the thermoplastic resin composition according to the presentinvention, the content of the component (B) in the total 100% by mass ofthe component (A) to the component (D) is 2% to 35% by mass, preferably5% to 34% by mass, and more preferably 8% to 33% by mass. When thecontent of the component (B) is more than or equal to theabove-described lower limit, the weld strength, the weld retention rate,the touch feeling (grip performance), and the slip resistance arefavorable. When the content of the component (B) is less than or equalto the above-described upper limit, the formability and the formedarticle appearance are favorable.

Regarding the thermoplastic resin composition according to the presentinvention, an absolute value of the difference between the content (% bymass) of the component (a1) in the total 100% by mass of the component(A) to the component (D) and the content (% by mass) of the component(B) (hereafter also referred to as “(a1)-(B)”) is within 15% by mass.When the (a1)-(B) is within 15% by mass, the formed article appearance,the wrinkling resistance, the wrinkling resistance against repetitions,and the weld strength are favorable. The (a1)-(B) is preferably within10% by mass, more preferably within 8.0% by mass, and further preferablywithin 6.0% by mass, particularly preferably within 5% by mass,especially preferably within 3.5% by mass, and most preferably 0% to2.0% by mass.

When the (a1)-(B) is within 15% by mass, either the component (a1) orthe component (B) may be larger in amount.

[Another Thermoplastic Resin (C)]

Another thermoplastic resin (C) contained in the thermoplastic resincomposition according to the present invention is a thermoplastic resinother than the component (A) and the component (B), and examples includeacrylonitrile-styrene-based resins, polycarbonate-based resins,polyacrylic resins, polybutylene-terephthalate-based resins,vinyl-chloride-based resins, polyamide-based resins, polyethylene-basedresins, polybutylene-based resins, and polyoxymethylene-based resins.

In particular, since the thermoplastic resin composition according tothe present invention is a resin expected to have adhesion to a casingresin of OA equipment and the like or to be used as just the casing andsince a balance between physical properties is readily achieved,acrylonitrile-styrene-based resins, polycarbonate-based resins,polyacrylic resins, and polybutylene-terephthalate-based resins areparticularly suitable for the another thermoplastic resin (C).

The thermoplastic resins (C) may be used alone, or at least two typesmay be used in combination.

Regarding the thermoplastic resin composition according to the presentinvention, the content of the component (C) in the total 100% by mass ofthe component (A) to the component (D) is 0.5% to 90% by mass,preferably 2% to 83% by mass, and more preferably 4% to 74% by mass.When the content of the component (C) is more than or equal to theabove-described lower limit, the formability is excellent. When thecontent of the component (C) is less than or equal to theabove-described upper limit, the weld strength and the weld retentionrate are excellent.

<Acrylonitrile-Styrene-Based Resin>

The acrylonitrile-styrene-based resin is a copolymer having structuralportions derived from an aromatic-vinyl-based monomer and avinyl-cyanide-based monomer.

Examples of the aromatic-vinyl-based monomer include styrene,α-methylstyrene, p-methylstyrene, vinyltoluene, t-butylstyrene,o-ethylstyrene, o-chlorostyrene, and o,p-dichlorostyrene. These may beused alone, or at least two types may be used in combination.

Examples of the vinyl-cyanide-based monomer include acrylonitrile,methacrylonitrile, and ethacrylonitrile. In particular, acrylonitrile ispreferable. The vinyl-cyanide-based monomer may also be used alone, orat least two types may also be used in combination.

The ratio of the aromatic-vinyl-based monomer unit to thevinyl-cyanide-based monomer unit in 100% by mass of theacrylonitrile-styrene-based resin is aromatic-vinyl-based monomerunit/vinyl-cyanide-based monomer unit=preferably 50% to 95% by mass/50%to 5% by mass, more preferably 60% to 85% by mass/40% to 15% by mass,and further preferably 65% to 80% by mass/35% to 20% by mass from theviewpoint of the formability and the formed article appearance.

The acrylonitrile-styrene-based resin may contain, in addition to thearomatic-vinyl-based monomer and the vinyl-cyanide-based monomer, othervinyl-cyanide-based monomer units copolymerizable with these in a rangeof 0% to 30% by mass. Examples of the other vinyl-based monomercopolymerizable with these include at least one of unsaturatedcarboxylic acid ester-based monomers, such as methyl (meth)acrylate,maleimide compounds, such as N-methylmaleimide, N-cyclohexylmaleimide,and N-phenylmaleimide, unsaturated dicarboxylic acids, such as maleicacid, unsaturated dicarboxylic acid anhydrides, such as maleicanhydride, and unsaturated amides, such as acrylamide, but thevinyl-based monomer is not limited to these. Of these, methyl(meth)acrylate, N-phenylmaleimide, and maleic anhydride are preferable.

The mass average molecular weight (Mw) of theacrylonitrile-styrene-based resin is preferably 50,000 to 400,000, morepreferably 70,000 to 350,000, and further preferably 90,000 to 300,000.

The molecular weight distribution (Mw/Mn) of theacrylonitrile-styrene-based resin is preferably 1.3 to 2.8, morepreferably 1.8 to 2.6, and further preferably 1.9 to 2.4.

The mass average molecular weight and the molecular weight distributionof the acrylonitrile-styrene-based resin can be measured as values interms of polystyrene on the basis of GPC.

The acrylonitrile-styrene-based resins may be used alone, or at leasttwo types of acrylonitrile-styrene-based resins that differ from eachother in monomer composition, molecular weight, or the like may be usedin combination.

<Polycarbonate Resin>

The polycarbonate resin is a polymer of a basic structure having acarbonate bond denoted by a general formula —(—O—R—O—C(═O)—)—.

Regarding the polycarbonate resin, aromatic polycarbonate resins havinga basic structure in which a carbon atom directly bonding to a carbonatebond is an aromatic carbon atom are preferable. In such an instance, inthe formula, R is generally an aromatic hydrocarbon group but may be anaromatic hydrocarbon group in which a hetero atom or a hetero bond isintroduced to provide various characteristics.

Typical examples of the aromatic polycarbonate resin include aromaticpolycarbonate resins produced from dihydroxyaryl compounds, such as2,2-bis(4-hydroxyphenyl)propane (bisphenol A).

Examples of the dihydroxyaryl compound include, in addition to bisphenolA, bis(hydroxyaryl)alkanes, such as bis(4-hydroxyphenyl)methane,1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane,2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)diphenylmethane,2,2-bis(4-hydroxy-3-methylphenyl)propane,1,1-bis(4-hydroxy-3-tert-butylphenyl)propane,2,2-bis(4-hydroxy-3-bromophenyl)propane,2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, and2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane;bis(hydroxyaryl)cycloalkanes, such as1,1-bis(4-hydroxyphenyl)cyclopentane and1,1-bis(4-hydroxyphenyl)cyclohexane; dihydroxydiaryl ethers, such as4,4′-dihydroxydiphenyl ether and 4,4′-dihydroxy-3,3′-dimethyldiphenylether; dihydroxydiaryl sulfides, such as 4,4′-dihydroxydiphenyl sulfideand 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide; dihydroxydiarylsulfoxides, such as 4,4′-dihydroxydiphenyl sulfoxide; anddihydroxydiaryl sulfones, such as 4,4′-dihydroxydiphenyl sulfone and4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone.

These may be used alone, or at least two types may be used incombination. In addition to these, piperazine, dipiperidyl hydroquinone,resorcin, 4,4′-dihydroxydiphenyls, and the like may be used incombination.

The above-described dihydroxydiaryl compound and a trivalent or higherphenol compound as described below may be used in combination. Examplesof the trivalent or higher phenol compound include phloroglucin,4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptene,2,4,6-trimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptane,1,3,5-tri-(4-hydroxyphenyl)-benzol, 1,1,1-tri-(4-hydroxyphenyl)-ethane,and 2,2-bis-(4,4-di(4-hydroxyphenyl)cyclohexyl)-propane.

There is no particular limitation regarding the viscosity averagemolecular weight (Mv) of the polycarbonate resin such as the aromaticpolycarbonate resin, and 15,000 to 40,000 is favorably adopted. If theviscosity average molecular weight (Mv) is less than 15,000, the impactresistance and the heat resistance tend to become poor. If the viscosityaverage molecular weight (Mv) is more than 40,000, the fluidity is poor,and a problem tends to occur in the formability. The viscosity averagemolecular weight (Mv) of the polycarbonate resin is more preferably16,000 to 35,000 and further preferably 18,000 to 30,000.

Therefore, for example, when the aromatic polycarbonate resin isproduced, it is preferable that an aromatic polycarbonate resin havingsuch a viscosity average molecular weight be produced by using theabove-described dihydroxydiaryl compound or the like and, as thesituation demands, a molecular weight adjustor, a catalyst, and thelike.

The viscosity average molecular weight [Mv] of the polycarbonate resinis a value calculated based on a viscosity formula expressed by Schnell,that is, η=1.23×10⁻⁴ Mv^(0.83), where methylene chloride is used as asolvent, and a limiting viscosity [η] (unit of dl/g) at a temperature of20° C. is determined by using Ubbelohde viscometer. The limitingviscosity [η] is a value calculated on the basis of a formula describedbelow, where the specific viscosity [ηsp] is measured at each solutionconcentration [C] (g/dl).

$\begin{matrix}{\eta = {\lim\limits_{c\rightarrow 0}{\eta_{sp}/c}}} & \left\lbrack {{Math}.1} \right\rbrack\end{matrix}$

Specific examples of the aromatic polycarbonate resin includecommercially available “Iupilon Series” and “NOVAREX Series” produced byMitsubishi Engineering-Plastics Corporation and “TARFLON Series”produced by Idemitsu Kosan Co., Ltd.

The polycarbonate resins such as the aromatic polycarbonate resin may beused alone, or at least two types of polycarbonate resins that differfrom each other in monomer composition, physical properties, or the likemay be used in combination. For example, at least two types ofpolycarbonate resins having viscosity average molecular weights thatdiffer from each other may be mixed so that the molecular weight isadjusted to the above-described favorable viscosity average molecularweight and be used.

<Polyacrylic Resin>

The polyacrylic resin is obtained by polymerizing a vinyl-based monomeror a vinyl-based monomer mixture containing(meth)acrylic-acid-ester-based monomer by using a known method. Thevinyl-based monomer mixture contains a (meth)acrylic-acid-ester-basedmonomer as an indispensable component and, as the situation demands, maycontain other vinyl-based monomers described below within the range of40% by mass.

Examples of the (meth)acrylic-acid-ester-based monomer include methyl(meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl(meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl(meth)acrylate, and phenyl (meth)acrylate.

Examples of the vinyl-based monomer other than the(meth)acrylic-acid-ester-based monomer include aromatic vinyl-basedmonomers, vinyl-cyanide-based monomers, maleimide-based monomers, and(meth)acrylic acid. Regarding the aromatic vinyl-based monomer and thevinyl-cyanide-based monomer, monomers akin to that contained in thevinyl-based monomer mixture (a2) can be used.

Examples of the maleimide-based monomer include N-alkylmaleimides(N-methylmaleimide, N-ethylmaleimide, N-n-propylmaleimide,N-i-propylmaleimide, N-n-butylmaleimide, N-i-butylmaleimide,N-t-butylmaleimide, and the like), N-cycloalkylmaleimides(N-cyclohexylmaleimide and the like), and N-arylmaleimides(N-phenylmaleimide, N-alkyl-substituted phenylmaleimide,N-chlorophenylmaleimide, and the like).

Of the polyacrylic resins, specific examples of the copolymerizationresins of methyl methacrylate and methyl acrylate include commerciallyavailable “PARAPET G” produced by Kuraray Co., Ltd., and “ACRYPET VH”and “ACRYPET MD” produced by Mitsubishi Chemical Corporation.

Specific examples of polyacrylic resins containing both the(meth)acrylic-acid-ester-based monomer unit and the maleimide-basedmonomer unit include commercially available “PARAPET SH-N” produced byKuraray Co., Ltd., and “POLYIMILEX PML203” produced by NIPPON SHOKUBAICO., LTD.

The polyacrylic resins may be used alone, or at least two types may beused in combination.

<Polybutylene-Terephthalate-Based Resin>

The polybutylene-terephthalate-based resin is a resin usually obtainedthrough a polycondensation reaction of terephthalic acid and/or aderivative thereof and 1,4-butanediol and/or a derivative thereof.Copolymerization products of other copolymerizable dicarboxylic acidsand/or derivatives thereof or glycols may also be used as thepolybutylene-terephthalate-based resin within the bound of not impairingthe object of the present invention.

Examples of the copolymerizable dicarboxylic acid include dicarboxylicacids, such as isophthalic acid, 2-chloroterephthalic acid,2,5-dichloroterephthalic acid, 2-methylterephthalic acid,4,4-stilbenedicarboxylic acid, 4,4-biphenyldicarboxylic acid,ortho-phthalic acid, 2,6-naphthalenedicarboxylic acid, bisbenzoic acid,bis(p-carboxyphenyl)methane, anthracenedicarboxylic acid, 4,4-diphenylether dicarboxylic acid, 4,4-diphenoxyethanedicarboxylic acid, adipicacid, sebacic acid, azelaic acid, dodecanedioic acid,1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid,and derivatives thereof. The copolymerizable dicarboxylic acids and/orderivatives thereof appropriately selected from, for example, thosedescribed above are used alone, or at least two types are used incombination.

Examples of the copolymerizable glycols include ethylene glycol,1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol,trans- or cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol, neopentyl glycol,1,5-pentanediol, 1,6-haxanediol, 1,4-cyclohexanedimethanol,1,3-cyclohexanedimethanol, decamethylene glycol, cyclohexanediol,p-xylenediol, bisphenol A, tetrabromobisphenol A, andtetrabromobisphenol-A-bis(2-hydroxyethyl ether). The copolymerizableglycols appropriately selected from, for example, those described aboveare used alone, or at least two types are used in combination.

The limiting viscosity of the polybutylene-terephthalate-based resin ispreferably 0.7 to 1.50 dl/g from the viewpoint of sufficiently ensuringthe fluidity and the formability of the thermoplastic resin compositionaccording to the present invention and the impact resistance of thethermoplastic resin formed article according to the present inventionformed by using the thermoplastic resin composition.

The limiting viscosity of the polybutylene-terephthalate-based resin ismeasured in a 1:1 (mass ratio) solution mixture of tetrachloroethane andphenol at 30° C.

Specific examples of the polybutylene-terephthalate-based resin includecommercially available “NOVADURAN” produced by MitsubishiEngineering-Plastics Corporation and “DURANEX” produced by POLYPLASTICSCO., LTD.

The polybutylene-terephthalate-based resins may be used alone, or atleast two types may be used in combination.

[Inorganic Compound (D)]

The thermoplastic resin composition according to the present inventioncontaining the inorganic compound (D) enables the formability to beimproved and enables the form of a product to be stabilized.

Examples of the inorganic compound (D) include metal fiber, aramidfiber, asbest, potassium titanate whisker, wollastonite, glass flake,glass beads, talc, mica, clay, calcium carbonate, barium sulfate,titanium oxide, and aluminum oxide.

The shape of the inorganic compound (D) is preferably flat-plate-like,linear, or scale-like. Of these, a plate-like shape or a scale-likeshape is more preferable from the viewpoint of the appearance, thewrinkling resistance against bending, and the repetitive bendingproperty.

The volume average particle diameter (MV) determined by a laserdiffraction method of the inorganic compound (D) is preferably 1 to 200μm, more preferably 2 to 120 μm, further preferably 10 to 80 μm, andparticularly preferably 15 to 40 μm.

When the volume average particle diameter (MV) of the inorganic compound(D) is more than or equal to the above-described lower limit, the weldstrength, the weld retention rate, the wrinkling resistance againstbending, and the repetitive bending property are favorable. When thevolume average particle diameter (MV) of the inorganic compound (D) isless than or equal to the above-described upper limit, the formability,the formed article appearance, and the weld retention rate arefavorable.

The ratio (aspect ratio) of the thickness to the volume average particlediameter (MV) of the inorganic compound (D) is preferably 5 to 150, morepreferably 10 to 120, and further preferably 40 to 90.

The reason is that when the aspect ratio is more than or equal to theabove-described lower limit, a balance between the formability, thewrinkling resistance against bending, and the repetitive bendingproperty is favorable. When the aspect ratio is less than or equal tothe above-described upper limit, the formed article appearance, the weldstrength, the weld retention rate, the touch feeling (grip performance),and the slip resistance are favorable.

The inorganic compounds (D) may be used alone, or at least two types maybe used in combination. Of these, titanium oxide, talc, mica, andcalcium carbonate are preferable, and in particular, mica is preferablefrom the viewpoint of the appearance, the wrinkling resistance againstbending, and the repetitive bending property.

Mica include dry-ground mica and wet-ground mica, and wet-ground mica ispreferable. In particular, wet-ground muscovite is preferable. Wetgrinding has higher utility value than dry grinding due to high purityand no influence being exerted on the appearance.

Regarding the thermoplastic resin composition according to the presentinvention, the content of the component (D) in the total 100% by mass ofthe component (A) to the component (D) is 0.5% to 20% by mass,preferably 2% to 18% by mass, and more preferably 3% to 15% by mass.When the content of the component (D) is more than or equal to theabove-described lower limit, the above-described effect due to using thecomponent (D) can be sufficiently obtained. When the content of thecomponent (D) is less than or equal to the above-described upper limit,the mechanical properties, the formed article appearance, and the likeare not impaired.

[Other Additives]

To improve the performance as a forming resin, various additives may beadded to the thermoplastic resin composition according to the presentinvention within the bound of not impairing the object of the presentinvention.

For example, as the situation demands, various stabilizers, such asantioxidants of hindered phenol base, sulfur-containing organic compoundbase, phosphorus-containing organic compound base, and the like, heatstabilizers of phenol base, acrylate base, and the like,transesterification inhibitors e.g. a mixture of monostearyl acidphosphate and distearyl acid phosphate, ultraviolet absorbers ofbenzotriazole base, benzophenone base, salicylate base, and the like,and light stabilizers of organic nickel base, hindered amine base, andthe like; lubricants, such as higher fatty acid metal salts and higherfatty acid amides; plasticizers, such as phthalic acid esters andphosphoric acid esters; flame retardants and flame retardantauxiliaries, such as halogen-containing compounds e.g. polybromodiphenylether, tetrabromobisphenol A, brominated epoxy oligomers, and brominatedpolycarbonate oligomers, phosphorus-based compounds, and antimonytrioxide; and carbon black, pigments, dyes, and the like may be added.

[Method for Producing Thermoplastic Resin Composition]

The thermoplastic resin composition according to the present inventionmay be produced by using various methods, for example, theabove-described components (A) to (D) and the above-described additiveswhich are used as the situation demands are melt-kneaded by using aBanbury mixer, a roll, or a single-screw or multi-screw extruder.

[Thermoplastic Resin Formed Article]

The thermoplastic resin formed article according to the presentinvention is obtained by forming the thermoplastic resin compositionaccording to the present invention by using a known forming method.

Examples of the forming method include an injection molding method, apress molding method, an extrusion molding method, a vacuum formingmethod, and a blow molding method.

The thermoplastic resin formed article according to the presentinvention produced by forming the thermoplastic resin compositionaccording to the present invention undergoes no peeling nor whiteningduring a forming process, acquires excellent appearance and mechanicalproperties, in particular, weld strength, has bending performance sothat no wrinkles occur during bending and so that the bending propertyis maintained against repetitions, and has slip resistance and high gripperformance.

The thermoplastic resin formed article according to the presentinvention may be used as a grip surface or parts of a casing of electricor electronic components, automobile components, machine mechanismcomponents, OA equipment, housing components of home electricappliances, general merchandise, housing construction materials, and thelike.

EXAMPLES

To further specifically explain the present invention, the descriptionwill be provided below with reference to the examples and thecomparative examples. These examples do not limit the present invention.“%” expresses % by mass, and “part” expresses part by mass, unlessotherwise specified.

The volume average particle diameter of the rubber-like polymer (a1) andthe graft rate of the rubber-containing graft copolymer (A) weremeasured as described in (1) and (2) below, respectively.

(1) Volume Average Particle Diameter

The volume average particle diameter of the rubber-like polymer (a1) ina latex was measured at room temperature by using “Microtrac UPA150”(trade name) produced by HONEYWELL. The unit is nm.

It is known that there is substantially no difference between the latexparticle diameter of the rubber-like polymer (a1) and the rubberparticle diameter of the rubber-like polymer (a1) in the resincomposition by using the rubber-like polymer (a1), and the former is inaccord with the latter.

(2) Graft Rate

The graft rate of the rubber-containing graft copolymer (A) iscalculated on the basis of a formula below.

graft rate (% by mass)={[(n)−(m)×L]/[(m)×L]}×100

In the above-described formula, n represents mass n (g) ofacetone-insoluble matters obtained by placing about 1 g [weighingcapacity: m (g)] of the rubber-containing graft copolymer (A) into 20 mlof acetone, performing shaking for 2 hours by using a shaker under atemperature condition of 25° C., and performing centrifugal separationfor 60 minutes by using a centrifuge (rotational speed: 23,000 rpm)under a temperature condition of 5° C. so as to separateacetone-insoluble matters and acetone-soluble matters from each other.

L represents the mass (g) of the rubber-like polymer (a1) contained inthe rubber-containing graft copolymer (A). The mass of the rubber-likepolymer (a1) may be determined by using a method for calculating fromthe polymerization proportion and the degree of polymerizationconversion, a method for determining based on the infrared absorptionspectrum, or the like.

Rubber-Containing Graft Copolymer (A) Synthesis Example 1: Production ofRubber-Containing Graft Copolymer (A1)

The interior of a reactor was replaced with nitrogen, and 120 parts ofpure water, 0.5 parts of glucose, 0.5 parts of sodium pyrophosphate,0.005 parts of ferrous sulfate, and 60 parts (in terms of solidcontents) of polybutadiene latex having a volume average particlediameter of 280 nm were charged, and the temperature in the reactor wasincreased to 65° C. while agitation was performed. The point in time ofthe internal temperature reaching 65° C. was assumed to be the start ofpolymerization, and 30 parts of styrene, 10 parts of acrylonitrile, and0.25 parts of a chain transfer agent, t-dodecylmercaptan mixture, werecontinuously added over 5 hours. Simultaneously, an aqueous solutioncomposed of a polymerization initiator, cumenehydroperoxide (0.2 parts),and potassium oleate was continuously added over 7 hours so as tocomplete a reaction. The resulting latex was mixed with 1 part of2,2′-methylenebis(4-methyl-6-t-butylphenol) relative to 100 parts oflatex solid contents. Subsequently, the latex was solidified withsulfuric acid, neutralized with sodium hydroxide, washed, filtered, anddried so as to obtain a powder-like rubber-containing graft copolymer(A1).

The rubber content of the rubber-containing graft copolymer (A1) was60%, and the graft rate was 55%.

Synthesis Example 2: Production of Rubber-Containing Graft Copolymer(A2)

A rubber-containing graft copolymer (A2) was produced by using the samemethod as the production of the rubber-containing graft copolymer (A1)of synthesis example 1 except that the amount of the polybutadiene latexhaving a volume average particle diameter of 280 nm charged was set tobe 40 parts (in terms of solid contents) and that the amount of styreneadded was changed to 45 parts, the amount of acrylonitrile added waschanged to 15 parts, and the amount of chain transfer agent,t-dodecylmercaptan mixture, was changed to 0.28 parts.

The rubber content of the rubber-containing graft copolymer (A2) was40%, and the graft rate was 95%.

[Thermoplastic Elastomer (B)]

Regarding a thermoplastic elastomer (B1), a hydrogenated block copolymer“DYNARON DR8903P” (trade name) (the styrene/butadiene mass ratio of thethermoplastic elastomer (B1) before hydrogenation was 35/65) produced byJSR Corporation, which is a styrene-ethylene-butylene-styrene copolymer(SEBS), was used.

The thermoplastic elastomer (B1) had an MFR (230° C., 21.2 N) of 10 g/10min and an MFR (200° C., 49.0 N) of 4 g/10 min.

Another Thermoplastic Resin (C) Synthesis Example 3: Production ofAcrylonitrile-Styrene-Based Resin (C1)

The interior of a reactor was replaced with nitrogen, and 120 parts ofwater, 0.002 parts of sodium alkylbenzenesulfonate, 0.5 parts ofpolyvinyl alcohol, 0.3 parts of azoisobutyronitrile, 0.5 parts oft-dodecylmercaptan, and a monomer mixture composed of 26 parts ofacrylonitrile and 74 parts of styrene were used, and the temperature wasincreased for 5 hours from a start temperature of 60° C. by heatingwhile a portion of styrene was successively added so as to reach 120° C.Further, the reaction was performed at 120° C. for 4 hours. Thereafter,polymerized material was removed so as to obtain anacrylonitrile-styrene-based resin (C1) in whichacrylonitrile/styrene=26/74 (mass ratio).

The mass average molecular weight (Mw) and the molecular weightdistribution (Mw/Mn) of the acrylonitrile-styrene-based resin (C1) interms of polystyrene were measured by using GPC (GPC: “GPC/V2000”produced by Waters, column: “Shodex AT-G+AT-806MS” produced by SHOWADENKO K.K.) and using o-dichlorobenzene (145° C.) as a solvent. As aresult, the mass average molecular weight (Mw) was 110,000, and themolecular weight distribution (Mw/Mn) was 2.3.

<Aromatic Polycarbonate Resin (C2)>

Regarding an aromatic polycarbonate resin (C2), “Iupilon S-2000F”(viscosity average molecular weight (Mv): 22,000) produced by MitsubishiEngineering-Plastics Corporation was used.

<Polyacrylic Resin (C3)>

Regarding a polyacrylic resin (C3), “ACRYPET VH5” produced by MitsubishiChemical Corporation was used.

<Polybutylene Terephthalate Resin (C4)>

Regarding polybutylene terephthalate resin (C4), “NOVADURAN 5020”(limiting viscosity (30° C.): 1.20 dl/g) produced by MitsubishiEngineering-Plastics Corporation was used.

[Inorganic Compound (D)]

Regarding an inorganic compound (D1), “A-21 (trade name)” (wet-groundmuscovite, volume average particle diameter of 22 μm, aspect ratio of70) produced by YAMAGUCHI MICA CO., LTD., was used.

Examples 1 to 8 and Comparative Examples 1 to 6

<Production of Thermoplastic Resin Composition>

Components (A), (B), (C), and (D) described in Tables 1A and 1B belowwere mixed at a mixing ratio described in Tables 1A and 1B. Thereafter,0.2 parts of ADK STAB “A-60 (trade name)”(tetrakis[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane)produced by ADEKA Corporation was mixed, and melt-kneading was performedby using Twin Screw Extruder (Model name “TEX44, Japan Steel Works,Ltd.”) at a barrel temperature of 220° C. so as to performpelletization. Formed articles (1) to (4) below were produced by usingthe resulting thermoplastic resin composition pellet and were subjectedto the measurement and the evaluation below. The results are describedin Tables 1A and 1B.

<Production of Formed Article (1)>

A test piece of 120 mm×80 mm×2 mm was produced by using an injectionmolding machine “IS100GN” (trade name) produced by TOSHIBA MACHINE CO.,LTD. under the conditions of a resin temperature of 220° C., a moldtemperature of 50° C., an injection rate of 40 mm/s, and an injectionpressure of 100 MPa. A leather grain mold (grain No.: TH-894) havingunevenness (the depth of a recessed portion was 100 μm) on the innersurface was used as a mold for forming.

<Production of Formed Article (2)>

A dumbbell test piece (without weld) having a gate on one side wasproduced by using an injection molding machine “J110AD-180H” (Modelname) produced by Japan Steel Works, Ltd., while the cylindertemperature was set to be 220° C., and the mold temperature was set tobe 50° C. Subsequently, a test piece (size: 80×10×4 mm) without a weldwas produced by cutting the central portion of the resulting dumbbelltest piece.

<Production of Formed Article (3)>

A dumbbell test piece with a weld was produced by using a mold capableof forming a weld at the center of the test piece having a gate at bothends and by using the injection molding machine “J110AD-180H” (Modelname) produced by Japan Steel Works, Ltd., while the cylindertemperature was set to be 220° C., and the mold temperature was set tobe 50° C. Subsequently, a test piece (size: 80×10×4 mm) with a weld atthe central portion was produced by cutting the central portion of theresulting dumbbell test piece with a weld at the central portion.

<Production of Formed Article (4)>

A dumbbell test piece (size: 80×10×4 mm) having a gate on one side wasproduced by using the injection molding machine “J110AD-180H” (Modelname) produced by Japan Steel Works, Ltd., while the cylindertemperature was set to be 220° C., and the mold temperature was set tobe 50° C.

<Measurement of Hardness>

The formed article (4) was used, and Rockwell hardness (hardness scalewas R-scale) at room temperature was measured in conformity with ISO2039.

<Measurement of Flexural Strength>

The formed article (2) was used, and flexural yield strength (FS0) wasmeasured in conformity with ISO 178. The unit of the measurement valueis MPa.

<Measurement of Flexural Strength of Weld Portion>

The formed article (3) was used, and flexural yield strength (FS1) wasmeasured in conformity with ISO 178. The unit of the measurement valueis MPa.

<Evaluation of Weld Strength Retention Rate>

Regarding the flexural yield strength without a weld (FS0) and theflexural yield strength of the weld portion (FS1) measured in conformitywith ISO 178, a weld strength retention rate (%) was determined by usinga formula below. It is indicated that a material having higher retentionrate has higher weld strength. Practically, 70% or more of retentionrate is necessary.

weld strength retention rate (%)=(FS1)/(FS0)×100

<Measurement of Flexural Modulus of Elasticity>

The formed article (2) was used, and flexural modulus of elasticity wasmeasured in conformity with ISO 178. The unit of the measurement valueis MPa.

<Measurement of Temperature of Deflection Under Load (Heat DeflectionTemperature: HDT)>

The formed article (4) was used, and a temperature of deflection underload was measured in conformity with ISO 75 (flatwise B method, load of1.82 MPa). The unit of the measurement value is ° C.

<Evaluation of Formed Article Appearance>

The formed article (1) was used, both the grain surface and the mirrorsurface were visually observed, and evaluation was performed on thebasis of the criteria described below.

◯: neither (i) flow mark nor (ii) peeling nor (iii) whitening occurred

Δ: one of (i) flow mark, (ii) peeling, and (iii) whitening occurred in aportion of the formed article

x: one of (i) flow mark, (ii) peeling, and (iii) whitening occurred onthe entire surface of the formed article

<Evaluation of Touch Feeling (Grip Feeling)>

The touch feeling when a finger was moved along the grain surface of theformed article (1) at normal temperature of 23° C. was evaluated on thebasis of the criteria described below.

◯: hard to slip

Δ: somewhat hard to slip

x: easy to slip

<Measurement of MIU Value (KES Texture Measurement)

The MIU value of the grain surface of the formed article (1) wasmeasured by using “Friction Tester KES-SE” (trade name) produced by KATOTECH CO., LTD. The MIU value (average frictional coefficient) is anindicator of slip resistance, and a higher value indicates higher slipresistance.

<Evaluation of Wrinkling Resistance Against Bending>

The formed article (1) was bent 20 degrees toward the opposite side(gloss surface side) of the grain surface, the bent side (gloss surfaceside) was visually observed, and evaluation was performed on the basisof the criteria described below.

◯: no wrinkles occurred

x: wrinkles occurred

<Evaluation of Wrinkling Resistance Against Repetitive Bending>

The formed article (1) was bent 20 degrees toward the opposite side(gloss surface side) of the grain surface and, thereafter, returned tothe original state. Further, the action of bending 20 degrees wererepeated 30 times. Subsequently, the bent side (gloss surface side) wasvisually observed, and evaluation was performed on the basis of thecriteria described below.

◯: no wrinkles occurred

Δ: some small wrinkles occurred

x: wrinkles occurred

<Formability Evaluation 1>

The releasability from the mold during forming of the formed article (1)was evaluated on the basis of the criteria described below.

◯: a non-defective product was automatically removed without sticking

Δ: a non-defective product was manually removed while sticking occurredto some extent

x: a non-defective product was not removed due to strong sticking

<Formability Evaluation 2>

Regarding deformation and discoloration due to an ejector pin duringforming of the formed article (1), the following items were examined andevaluated on the basis of the criteria described below.

Presence or absence of deformation (deformation (defect) such asbreakage, tear, and peeling) and discoloration (whitening and the like)around traces of 4 ejector pins on the back of the grain surface of theformed article (1)

◯: a non-defective product was removed with neither deformation nordiscoloration

Δ: deformation did not occur but discoloration occurred

x: deformation and discoloration occurred

TABLE 1A Example 1 2 3 4 5 6 7 8 Thermoplastic Component (A)* A1(60) %by mass 50 20 25 56 60 64 62 resin A2(40) % by mass 60 compositionComponent (B) B1 % by mass 30 15 10 34 30 30 25 25 proportion Component(C) C1 % by mass 15 1 8 C2 % by mass 60 60 C3 % by mass 10 C4 % by mass5 5 Component (D) D1 % by mass 5 5 5 5 5 5 5 5 Total of components (A) %by mass 100 100 100 100 100 100 100 100 to (D) Content of component (a1)in total of % by mass 30.0 12.0 15.0 33.6 36.0 38.4 37.2 24.0 components(A) to (D) (a1) − (B) % by mass 0.0 −3.0 5.0 −0.4 6.0 8.4 12.2 −1.0Evaluation Rockwell hardness R 5 67 67 23 25 4 5 17 result Flexuralstrength MPa 10 32 29 5 6 7 9 25 Flexural strength (weld MPa 9 25 24 5 67 6 22 portion) Weld strength retention % 90 78 83 100 100 100 67 88rate Flexural modulus of MPa 350 1060 900 110 140 100 180 650 elasticityTemperature of ° C. 56 105 106 50 52 50 54 65 deflection under loadFormed article ○ ○ ○ ○ ○ ○ ○ Δ appearance Touch feeling (grip ○ ○ ○ ○ ○○ ○ ○ feeling) MIU value (slip 0.7 0.3 0.3 0.8 0.7 0.7 0.6 0.3resistance) Wrinkling resistance ○ ○ ○ ○ ○ Δ Δ ○ against bendingRepeatability ○ ○ ○ ○ ○ Δ Δ Δ Formability Releasability ○ ○ ○ ○ ○ ○ ○ ○from mold Deformation ○ ○ ○ ○ ○ ○ Δ ○ due to ejector pin * numericalvalues in parentheses represent content (% by mass of rubber-likepolymer (a1) in rubber-containing graft copolymer (A)

TABLE IB Comparative example 1 2 3 4 5 6 Thermoplastic Component (A)*A1(60) % by mass 50 20 resin composition A2(40) % by mass 15 15 60 15proportion Component (B) B1 % by mass 35 35 25 30 15 35 Component (C) C1% by mass 50 5 20 45 C2 % by mass 50 65 C3 % by mass 10 C4 % by massComponent (D) D1 % by mass 5 Total of components (A) to (D) % by mass100 100 100 100 100 100 Content of component (a1) in total of components(A) to (D) % by mass 6.0 6.0 24.0 30.0 12.0 6.0 (a1) − (B) % by mass−29.0 −29.0 −1.0 0.0 −3.0 −29.0 Evaluation result Rockwell hardness R 4043 15 4 60 42 Flexural strength MPa 28 29 22 12 34 30 Flexural strength(weld portion) MPa 10 9 17 10 13 11 Weld strength retention rate % 36 3177 83 38 40 Flexural modulus of elasticity MPa 840 840 600 340 990 900Temperature of deflection under load ° C. 59 80 64 54 104 61 Formedarticle appearance Δ Δ Δ ○ ○ Δ Touch feeling (grip feeling) ○ ○ ○ ○ ○ ○MIU value (slip resistance) 0.6 0.6 0.3 0.8 0.4 0.6 Wrinkling resistanceagainst bending x x x Δ x x Repeatability x x x x x x FormabilityReleasability x x Δ Δ Δ Δ from mold Deformation x x Δ x Δ Δ due toejector pin * numerical values in parentheses represent content (% bymass) of rubber-like polymer (a ) in rubber- containing graft copolymer(A)

The following is clarified from Tables 1A and 1B.

In examples 1 to 8 in which the thermoplastic resin compositionaccording to the present invention was used, not only excellenthardness, flexural modulus of elasticity, and formed article appearancewere exhibited, but also excellent touch feeling (grip feeling), slipresistance (MIU value), wrinkling resistance against bending, andwrinkling resistance against repetitive bending were exhibited.

In comparative examples 1 to 5 in which the inorganic compound (D) wasnot contained and in which the requirements of the present inventionwere not satisfied, poor performance, such as weld strength, appearance,wrinkling resistance against bending, and repetition characteristicsthereof, were exhibited.

In comparative example 6 in which the inorganic compound (D) wascontained but in which (a1)-(B) was more than 15% by mass, poorperformance, such as weld strength, wrinkling resistance againstbending, and repetition characteristics thereof, were exhibited.

Although the present invention has been described in detail by way ofthe specific modes, it is apparent for those skilled in the art thatvarious changes can be made without departing from the spirit and scopeof the present invention.

The present application is based on Japanese Patent Application No.2020-069838 filed on Apr. 8, 2020 and Japanese Patent Application No.2020-140258 filed on Aug. 21, 2020, the entire contents of which areincorporated herein by reference.

INDUSTRIAL APPLICABILITY

The thermoplastic resin formed article according to the presentinvention in which the thermoplastic resin composition according to thepresent invention is used has excellent mechanical strength, formedarticle appearance, slip resistance of the surface, and favorable touchfeeling such as grip feeling and, therefore, is suitable for use as anarticle which has to be manually operated or be prevented from readilyslipping out of a hand, and is capable of providing a product having arepetitive bending property, slip resistance, and high grip performance.Further, the utility value is very high, for example, the thermoplasticresin formed article serves as not only a grip for a hand, but also as amember of a ground surface of a personal computer, a printer, or thelike so as to enable a non-slip effect to be realized.

What is claimed is:
 1. A thermoplastic resin composition comprising 7%to 64% by mass of rubber-containing graft copolymer (A), 2% to 35% bymass of thermoplastic elastomer (B), 0.5% to 90% by mass ofpolycarbonate-based resins (C), and 0.5% to 20% by mass of inorganiccompound (D) having volume average particle diameter (MV) of 1 to 200 μm(where a total of (A), (B), (C), and (D) (hereafter referred to as“total of a component (A) to a component (D)”) is 100% by mass), whereinthe rubber-containing graft copolymer (A) is a graft copolymer in which35 to 80 parts by mass of rubber-like polymer selected from diene-basedrubber, acrylic rubber, and ethylene-based rubber is graft-polymerizedwith 20 to 65 parts by mass of vinyl-based monomer mixture containing anaromatic-vinyl-based monomer and a vinyl-cyanide-based monomer (where atotal of the rubber-like polymer and the vinyl-based monomer mixture is100% by mass), the thermoplastic elastomer (B) is a styrene-basedelastomer which is a block copolymer containing at least one polymerblock P of an aromatic vinyl compound and at least one polymer block Qof a conjugated diene compound and/or a hydrogenation product thereof,and a difference between the content (% by mass) of the rubber-likepolymer in the total 100% by mass of the component (A) to the component(D) and the content (% by mass) of the thermoplastic elastomer (B) iswithin 15% by mass.
 2. The thermoplastic resin composition according toclaim 1, wherein the volume average particle diameter of the rubber-likepolymer is 100 to 1,500 nm, the ratio of the aromatic-vinyl-basedmonomer to the vinyl-cyanide-based monomer in 100% by mass of thevinyl-based monomer mixture is aromatic-vinyl-basedmonomer/vinyl-cyanide-based monomer=50% to 95% by mass/50% to 5% bymass, and the graft rate of the rubber-containing graft copolymer (A) is20% to 100% by mass.
 3. The thermoplastic resin composition according toclaim 1, wherein the MFR (200° C., 49.0 N) of the thermoplasticelastomer (B) is 1 to 25 g/10 min, and the MFR (230° C., 21.2 N) is 3 to30 g/10 min.
 4. The thermoplastic resin composition according to claim1, wherein the thermoplastic elastomer (B) is the styrene-basedelastomer having a content of the polymer block P of 5% to 60% by mass,and a content of the polymer block Q of 95% to 40% by mass.
 5. Thethermoplastic resin composition according to claim 1, wherein theinorganic compound (D) is muscovite.
 6. A thermoplastic resin formedarticle produced by forming the thermoplastic resin compositionaccording to claim
 1. 7. The thermoplastic resin composition accordingto claim 2, wherein the MFR (200° C., 49.0 N) of the thermoplasticelastomer (B) is 1 to 25 g/10 min, and the MFR (230° C., 21.2 N) is 3 to30 g/10 min.
 8. The thermoplastic resin composition according to claim2, wherein the thermoplastic elastomer (B) is the styrene-basedelastomer having a content of the polymer block P of 5% to 60% by mass,and a content of the polymer block Q of 95% to 40% by mass.
 9. Thethermoplastic resin composition according to claim 3, wherein thethermoplastic elastomer (B) is the styrene-based elastomer having acontent of the polymer block P of 5% to 60% by mass, and a content ofthe polymer block Q of 95% to 40% by mass.
 10. A thermoplastic resinformed article produced by forming the thermoplastic resin compositionaccording to claim 2.